Search results for: in situ Raman Spectroscopy

Authors: Dorottya Guban, Irina Borbath, Istvan Bakos, Peter Nemeth, Andras Tompos

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One of the greatest challenges of the implementation of polymer electrolyte membrane fuel cells (PEMFCs) is to find active and durable electrocatalysts. The cell performance is always limited by the oxygen reduction reaction (ORR) on the cathode since it is at least 6 orders of magnitude slower than the hydrogen oxidation on the anode. Therefore high loading of Pt is required. Catalyst corrosion is also more significant on the cathode, especially in case of mobile applications, where rapid changes of loading have to be tolerated. Pt-Sn bulk alloys and SnO2-decorated Pt3Sn nanostructures are among the most studied bimetallic systems for fuel cell applications. Exclusive formation of supported Sn-Pt alloy phases with different Pt/Sn ratios can be achieved by using controlled surface reactions (CSRs) between hydrogen adsorbed on Pt sites and tetraethyl tin. In this contribution our results for commercial and a home-made 20 wt.% Pt/C catalysts modified by tin anchoring via CSRs are presented. The parent Pt/C catalysts were synthesized by modified NaBH4-assisted ethylene-glycol reduction method using ethanol as a solvent, which resulted either in dispersed and highly stable Pt nanoparticles or evenly distributed raspberry-like agglomerates according to the chosen synthesis parameters. The 20 wt.% Pt/C catalysts prepared that way showed improved electrocatalytic performance in the ORR and stability in comparison to the commercial 20 wt.% Pt/C catalysts. Then, in order to obtain Sn-Pt/C catalysts with Pt/Sn= 3 ratio, the Pt/C catalysts were modified with tetraethyl tin (SnEt4) using three and five consecutive tin anchoring periods. According to in situ XPS studies in case of catalysts with highly dispersed Pt nanoparticles, pre-treatment in hydrogen even at 170°C resulted in complete reduction of the ionic tin to Sn0. No evidence of the presence of SnO2 phase was found by means of the XRD and EDS analysis. These results demonstrate that the method of CSRs is a powerful tool to create Pt-Sn bimetallic nanoparticles exclusively, without tin deposition onto the carbon support. On the contrary, the XPS results revealed that the tin-modified catalysts with raspberry-like Pt agglomerates always contained a fraction of non-reducible tin oxide. At the same time, they showed increased activity and long-term stability in the ORR than Pt/C, which was assigned to the presence of SnO2 in close proximity/contact with Pt-Sn alloy phase. It has been demonstrated that the content and dispersion of the fcc Pt3Sn phase within the electrocatalysts can be controlled by tuning the reaction conditions of CSRs. The bimetallic catalysts displayed an outstanding performance in the ORR. The preparation of a highly dispersed 20Pt/C catalyst permits to decrease the Pt content without relevant decline in the electrocatalytic performance of the catalysts.

Keywords: anode catalyst, cathode catalyst, controlled surface reactions, oxygen reduction reaction, PtSn/C electrocatalyst

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Authors: Cahya Wimar Wicaksono, Reynara Davin Chen, Alvian Kristianto Santoso

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Grasberg Cu-Au ore deposit as one of the biggest porphyry deposits located in Papua Province, Indonesia produced by several intrusion that restricted by Heavy Sulphide Zone (HSZ) in peripheral. HSZ is the rock that becomes the contact between Grassberg Igneous Complex (GIC) with sedimentary and igneous rock outside, which is rich in sulphide minerals such as pyrite ± pyrrhotite. This research is to obtain the characteristic of HSZ based on geotechnical, geochemical and mineralogy aspect and those implication for daily mining operational activities. Method used in this research are geological and alteration mapping, core logging, FAA (Fire Assay Analysis), AAS (Atomic absorption spectroscopy), RQD (Rock Quality Designation) and rock water content. Data generated from methods among RQD data, mineral composition and grade, lithological and structural geology distribution in research area. The mapping data show that HSZ material characteristics divided into three type based on rocks association, there are near igneous rocks, sedimentary rocks and on HSZ area. And also divided based on its location, north and south part of research area. HSZ material characteristic consist of rock which rich of pyrite ± pyrrhotite, and RQD range valued about 25%-100%. Pyrite ± pyrrhotite which outcropped will react with H₂O and O₂ resulting acid that generates corrosive effect on steel wire and rockbolt. Whereas, pyrite precipitation proses in HSZ forming combustible H₂S gas which is harmful during blasting activities. Furthermore, the impact of H₂S gas in blasting activities is forming poison gas SO₂. Although HSZ high grade Cu-Au, however those high grade Cu-Au rich in sulphide components which is affected in flotation milling process. Pyrite ± pyrrhotite in HSZ will chemically react with Cu-Au that will settle in milling process instead of floating.

Keywords: combustible, corrosive, heavy sulphide zone, pyrite ± pyrrhotite

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Authors: M. Nerantzaki, I. Koliakou, D. Bikiaris

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This study evaluates the hypothesis that the incorporation of fibrous hydroxyapatite nanoparticles (nHA) with high crystallinity and high aspect ratio, synthesized by hydrothermal method, into Poly(butylene succinate) (PBSu), improves the bioactivity of the aliphatic polyester and affects new bone growth inhibiting resorption and enhancing bone formation. Hydroxyapatite nanorods were synthesized using a simple hydrothermal procedure. First, the HPO42- -containing solution was added drop-wise into the Ca2+-containing solution, while the molar ratio of Ca/P was adjusted at 1.67. The HA precursor was then treated hydrothermally at 200°C for 72 h. The resulting powder was characterized using XRD, FT-IR, TEM, and EDXA. Afterwards, PBSu nanocomposites containing 2.5wt% (nHA) were prepared by in situ polymerization technique for the first time and were examined as potential scaffolds for bone engineering applications. For comparison purposes composites containing either 2.5wt% micro-Bioglass (mBG) or 2.5wt% mBG-nHA were prepared and studied, too. The composite scaffolds were characterized using SEM, FTIR, and XRD. Mechanical testing (Instron 3344) and Contact Angle measurements were also carried out. Enzymatic degradation was studied in an aqueous solution containing a mixture of R. Oryzae and P. Cepacia lipases at 37°C and pH=7.2. In vitro biomineralization test was performed by immersing all samples in simulated body fluid (SBF) for 21 days. Biocompatibility was assessed using rat Adipose Stem Cells (rASCs), genetically modified by nucleofection with DNA encoding SB100x transposase and pT2-Venus-neo transposon expression plasmids in order to attain fluorescence images. Cell proliferation and viability of cells on the scaffolds were evaluated using fluoresce microscopy and MTT (3-(4,5-dimethylthiazol-2-yl)-2,5 diphenyltetrazolium bromide) assay. Finally, osteogenic differentiation was assessed by staining rASCs with alizarine red using cetylpyridinium chloride (CPC) method. TEM image of the fibrous HAp nanoparticles, synthesized in the present study clearly showed the fibrous morphology of the synthesized powder. The addition of nHA decreased significantly the contact angle of the samples, indicating that the materials become more hydrophilic and hence they absorb more water and subsequently degrade more rapidly. In vitro biomineralization test confirmed that all samples were bioactive as mineral deposits were detected by X-ray diffractometry after incubation in SBF. Metabolic activity of rASCs on all PBSu composites was high and increased from day 1 of culture to day 14. On day 28 metabolic activity of rASCs cultured on samples enriched with bioceramics was significantly decreased due to possible differentiation of rASCs to osteoblasts. Staining rASCs with alizarin red after 28 days in culture confirmed our initial hypothesis as the presence of calcium was detected, suggesting osteogenic differentiation of rACS on PBSu/nHAp/mBG 2.5% and PBSu/mBG 2.5% composite scaffolds.

Keywords: biomaterials, hydroxyapatite nanorods, poly(butylene succinate), scaffolds

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Authors: Federica Laface, Cristina Pedà, Francesco Longo, Francesca de Domenico, Riccardo Minichino, Pierpaolo Consoli, Pietro Battaglia, Silvestro Greco, Teresa Romeo

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Plastics pollution represents one of the most important threats to marine biodiversity. In the last decades, different species are investigated to evaluate the extent of the plastic ingestion phenomenon. Even if the cephalopods play an important role in the food chain, they are still poorly studied. The aim of this research was to investigate the plastic ingestion in two commercial cephalopod species from the southern Tyrrhenian Sea: the common octopus, Octopus vulgaris (n=6; mean mantle length ML 10.7 ± 1.8) and the common cuttlefish, Sepia officinalis (n=13; mean ML 13.2 ± 1.7). Plastics were extracted from the filters obtained by the chemical digestion of cephalopods gastrointestinal tracts (GITs), using 10% potassium hydroxide (KOH) solution in a 1:5 (w/v) ratio. Once isolated, particles were photographed, measured, and their size class, shape and color were recorded. A total of 81 items was isolated from 16 of the 19 examined GITs, representing a total occurrence (%O) of 84.2% with a mean value of 4.3 ± 8.6 particles per individual. In particular, 62 plastics were found in 6 specimens of O. vulgaris (%O=100) and 19 particles in 10 S. officinalis (%O=94.7). In both species, the microplastics size class was the most abundant (93.8%). Plastic items found in O. vulgaris were mainly fibers (61%) while fragments were the most frequent in S. officinalis (53%). Transparent was the most common color in both species. The analysis will be completed by Fourier transform infrared (FT-IR) spectroscopy technique in order to identify polymers nature. This study reports preliminary data on plastic ingestion events in two cephalopods species and represents the first record of plastic ingestion by the common octopus. Microplastic items detected in both common octopus and common cuttlefish could derive from secondary and/or accidental ingestion events, probably due to their behavior, feeding habits and anatomical features. Further studies will be required to assess the effect of marine litter pollution in these ecologically and commercially important species.

Keywords: cephalopods, GIT analysis, marine pollution, Mediterranean sea, microplastics

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Authors: Sanjeev Gupta, Ankit Prabhakar, K. Rajkumar Singh

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Sunni Dam Hydroelectric Project (382 MW) is a run of river type development with an underground powerhouse, proposed to harness the hydel potential of river Satluj in Himachal Pradesh, India. The project is located in the inner lesser Himalaya between Dhauladhar Range in the south and the higher Himalaya in the north. The project comprises two large underground caverns, a Powerhouse cavern (171m long, 22.5m wide and 51.2m high) and another transformer hall cavern (175m long, 18.7m wide and 27m high) and the rock pillar between the two caverns is 50m. The highly jointed, fractured, anisotropic rock mass is a key challenge in Himalayan geology for an underground structure. The concern for the stability of rock mass increases when weak/shear zones are encountered in the underground structure. In the Sunni Dam project, 1.7m to 2m thick weak/shear zone comprising of deformed, weak material with gauge has been encountered in powerhouse cavern at 70m having dip direction 325 degree and dip amount 38 degree which also intersects transformer hall at initial reach. The rock encountered in the powerhouse area is moderate to highly jointed, pink quartz arenite belonging to the Khaira Formation, a transition zone comprising of alternate grey, pink & white quartz arenite and shale sequence and dolomite at higher reaches. The rock mass is intersected by mainly 3 joint sets excluding bedding joints and a few random joints. The rock class in powerhouse mainly varies from poor class (class IV) to lower order fair class (class III) and in some reaches, very poor rock mass has also been encountered. To study the stability of the underground structure in weak/shear rock mass, a 3D numerical model analysis has been carried out using RS3 software. Field studies have been interpreted and analysed to derive Bieniawski’s RMR, Barton’s “Q” class and Geological Strength Index (GSI). The various material parameters, in-situ characteristics have been determined based on tests conducted by Central Soil and Materials Research Station, New Delhi. The behaviour of the cavern has been studied by assessing the displacement contours, major and minor principal stresses and plastic zones for different stage excavation sequences. For optimisation of the support system, the stability of the powerhouse cavern with different powerhouse orientations has also been studied. The numerical modeling results indicate that cavern will not likely face stress governed by structural instability with the support system to be applied to the crown and side walls.

Keywords: 3D analysis, Himalayan geology, shear zone, underground power house

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Authors: Mohamed dammak

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Great attention has been paid to the design and synthesis of novel organic-inorganic compounds in recent decades because of their structural variety and the large diversity of atomic arrangements. In this work, the structure for the novel dimethyl aminopyridine tetrachlorocobaltate (C₇H₁₁N₂)₂CoCl₄ prepared by the slow evaporation method at room temperature has been successfully discussed. The X-ray diffraction results indicate that the hybrid material has a triclinic structure with a P space group and features a 0D structure containing isolated distorted [CoCl₄]2- tetrahedra interposed between [C7H11N²⁻]+ cations forming planes perpendicular to the c axis at z = 0 and z = ½. The effect of the synthesis conditions and the reactants used, the interactions between the cationic planes, and the isolated [CoCl4]2- tetrahedra are employing N-H...Cl and C-H…Cl hydrogen bonding contacts. The inspection of the Hirshfeld surface analysis helps to discuss the strength of hydrogen bonds and to quantify the inter-contacts. A phase transition was discovered by thermal analysis at 390 K, and comprehensive dielectric research was reported, showing a good agreement with thermal data. Impedance spectroscopy measurements were used to study the electrical and dielectric characteristics over a wide range of frequencies and temperatures, 40 Hz–10 MHz and 313–483 K, respectively. The Nyquist plot (Z" versus Z') from the complex impedance spectrum revealed semicircular arcs described by a Cole-Cole model. An electrical circuit consisting of a link of grain and grain boundary elements is employed. The real and imaginary parts of dielectric permittivity, as well as tg(δ) of (C₇H₁₁N₂)₂CoCl₄ at different frequencies, reveal a distribution of relaxation times. The presence of grain and grain boundaries is confirmed by the modulus investigations. Electric and dielectric analyses highlight the good protonic conduction of this material.

Keywords: organic-inorganic, phase transitions, complex impedance, protonic conduction, dielectric analysis

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Authors: Alba Barbara-i-Molinero, Rosalia Cascon-Pereira, Ana Beatriz Hernandez

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Students’ transitions from high school to the university have been challenged by the lack of continuity between both contexts. This mismatch directly affects students by generating feelings of anxiety and uncertainty, which increases the dropout rates and reduces students’ academic success. This discontinuity emanates because ‘transitions concern a restructuring of what the person does and who the person perceives him or herself to be’. Hence, identity becomes essential in these transitions. Generally, identity is the answer to questions such as who am I? or who are we? This is integrated by personal identity, and as many social identities as groups, the individual feels he/she is a part. A case in point to construct a social identity is the identification with a profession. For this reason, a way to lighten the generated tension during transitions is applying strategies orientated to enhance students’ professional identity in their point of entry to the higher education institution. That would create a sense of continuity between high school and higher education contexts, increasing their Professional Identity Strength. To develop the strategies oriented to enhance students Professional Identity, it is important to analyze what influences it. There exist several influencing factors that influence Professional Identity (e.g., professional status, the recommendation of family and peers, the academic environment, or the chosen bachelor degree). There is a gap in the literature analyzing the impact of these factors on more than one bachelor degree. In this regards, our study takes an additional step with the aim of evaluating the influence of several factors on Professional Identity using a cohort of university students from multiple degrees between the ages of 17-19 years. To do so, we used hierarchical regression analyses to assess the impact of the following factors: External Motivation Conditionals (EMC), Educational Experience Conditionals (EEC) and Personal Motivational Conditional (PMP). After conducting the analyses, we found that the assessed factors influenced students’ professional identity differently according to their bachelor degree and discipline. For example, PMC and EMC positively affected science students, while architecture, law and economics and engineering students were just influenced by PMC. Basing on that influences, we proposed three different strategies aimed to enhance students’ professional identity, in the short and long term. These strategies are: to enhance students’ professional identity before the incorporation to university through campuses and icebreaker activities; to apply recruitment strategies aimed to provide realistic information of the bachelor degree; and to incorporate different activities, such as in-vitro, in situ and self-directed activities aimed to enhance longitudinally students’ professional identity from the university. From these results, theoretical contributions and practical implications arise. First, we contribute to the literature by identifying which factors influence students from different bachelor degrees since there is still no evidence. And, second, using as a benchmark the obtained results, we contribute from a practical perspective, by proposing several alternative strategies to increase students’ professional identity strength aiming to lighten their transition from high school to higher education.

Keywords: professional identity, higher education, educational strategies , students

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Authors: Sanjay Singh, Karunanithi Priyanka, Ramoji Kosuru, Raju Prasad Sharma

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Herbal drugs are well known for their mixed pharmacological activities with the benefit of no harmful side effects. The use of herbal drugs is limited because of their higher dose requirement, frequent drug administration, poor bioavailability of phytochemicals and delayed onset of action. Ficus religiosa, a potent anti-oxidant plant useful in the treatment of diabetes and cancer was selected for the study. Solid lipid nanoparticles (SLN) of Ficus religiosa extract was developed for the enhancement in oral bioavailability of stigmasterol and β-sitosterol-d-glucoside, principal components present in the extract. Hot homogenization followed by ultrasonication method was used to develop extract loaded SLN. Developed extract loaded SLN were characterized for particle size, PDI, zeta potential, entrapment efficiency, in vitro drug release and kinetics, fourier transform infra-red spectroscopy, differential scanning calorimetry, powder X-ray diffractrometry and stability studies. Entrapment efficiency of optimized extract loaded SLN was found to be 68.46 % (56.13 % of stigmasterol and 12.33 % of β-sitosteryl-d-glucoside, respectively). RP HPLC method development was done for simultaneous estimation of stigmasterol and β-sitosterol-d-glucoside in Ficus religiosa extract in rat plasma. Bioavailability studies were carried out for extract in suspension form and optimized extract loaded SLN. AUC of stigmasterol and β-sitosterol-d-glucoside were increased by 6.7-folds by 9.2-folds, respectively in rats treated with extract loaded SLN compared to extract suspension. Also, Cmax of stigmasterol and β-sitosterol-d-glucoside were increased by 4.3-folds by 3.9-folds, respectively in rats treated with extract loaded SLN compared to extract suspension. Mean residence times (MRT) for stigmasterol were found to be 12.3 ± 0.67 hours from extract and 7.4 ± 2.1 hours from SLN and for β-sitosterol-d-glucoside, 10.49 ± 2.9 hours from extract and 6.4 ± 0.3 hours from SLN. Hence, it was concluded that SLN enhanced the bioavailability and reduced the MRT of stigmasterol and β-sitosterol-d-glucoside in Ficus religiosa extract which in turn may lead to reduction in dose of Ficus religiosa extract, prolonged duration of action and also enhanced therapeutic efficacy.

Keywords: Ficus religiosa, phytosterolins, bioavailability, solid lipid nanoparticles, stigmasterol and β-sitosteryl-d-glucoside

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Authors: J. W. Choi, S. Y. Cho, H. J. Lee, W. Z. Oh, S. J. Choi

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Ionic liquids (ILs), which is alternative to conventional organic solvent, were used for extraction of Cs ions. ILs, as useful environment friendly green solvents, have been recently applied as replacement for traditional volatile organic compounds (VOCs) in liquid/liquid extraction of heavy metal ions as well as organic and inorganic species and pollutants. Thus, Ionic liquids were used for extraction of Cs ions from the liquid radioactive waste. In most cases, Cs ions present in radioactive wastes in very low concentration, approximately less than 1ppm. Therefore, unlike established extraction system the required amount of ILs as extractant is comparatively very small. This extraction method involves cation exchange mechanism in which Cs ion transfers to the organic phase and binds to one crown ether by chelation in exchange of single ILs cation, IL_cation+, transfer to the aqueous phase. In this extraction system showed solid-liquid separation in which the Ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonly)imide (C2mimTf2N) and the crown ether Dicyclohexano-18-crown-6 (DCH18C6) both were used here in very little amount as solvent and as extractant, respectively. 30 mM of CsNO3 was used as simulated waste solution cesium ions. Generally, in liquid-liquid extraction, the molar ratio of CE:Cs+:ILs was 1:5~10:>100, while our applied molar ratio of CE:Cs+:ILs was 1:2:1~10. The quantity of CE and Cs ions were fixed to 0.6 and 1.2 mmol, respectively. The phenomenon of precipitation showed two kinds of separation: solid-liquid separation in the ratio of 1:2:1 and 1:2:2; solid-liquid-liquid separation (3 phase) in the ratio of 1:2:5 and 1:2:10. In the last system, 3 phases were precipitate-ionic liquids-aqueous. The precipitate was verified to consist of Cs+, DCH18C6, Tf2N- based on the cation exchange mechanism. We analyzed precipitate using scanning electron microscopy with X-ray microanalysis (SEM-EDS), an elemental analyser, Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC). The experimental results showed an easy extraction method and confirmed the composition of solid precipitate. We also obtained information that complex formation ratio of Cs+ to DCH18C6 is 0.88:1 regardless of C2mimTf2N quantities.

Keywords: extraction, precipitation, solid-liquid seperation, ionic liquid, precipitate

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Authors: Burcu Doymus, Fatma N. Kok, Sakip Onder

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Titanium and titanium-based materials are commonly used to replace or regenerate the injured or lost tissues because of accidents or illnesses. Hospital infections and strong bond formation at the implant-tissue interface are directly affecting the success of the implantation as weak bonding with the native tissue and hospital infections lead to revision surgery. The purpose of the presented study is to modify the surface of the titanium substrates with nano/microspheres for local drug delivery and to prevent hospital infections. Firstly, titanium surfaces were silanized with APTES (3-Triethoxysilylpropylamine) following the negatively charged oxide layer formation. Then characterization studies using Scanning Electron Microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were done on the modified surfaces. Secondly, microspheres/nanospheres were prepared with chitosan that is a natural polymer and having valuable properties such as non-toxicity, high biocompatibility, low allergen city and biodegradability for biomedical applications. Antibiotic (ciprofloxacin) loaded micro/nanospheres have been fabricated using emulsion cross-linking method and have been immobilized onto the titanium surfaces with different immobilization techniques such as covalent bond and entrapment. Optimization studies on size and drug loading capacities of micro/nanospheres were conducted before the immobilization process. Light microscopy and SEM were used to visualize and measure the size of the produced micro/nanospheres. Loaded and released drug amounts were determined by using UV- spectrophotometer at 278 nm. Finally, SEM analysis and drug release studies on the micro/nanospheres coated Ti surfaces were done. As a conclusion, it was shown that micro/nanospheres were immobilized onto the surfaces successfully and drug release from these surfaces was in a controlled manner. Moreover, the density of the micro/nanospheres after the drug release studies was higher on the surfaces where the entrapment technique was used for immobilization. Acknowledgement: This work is financially supported by The Scientific and Technological Research Council Of Turkey (Project # 217M220)

Keywords: chitosan, controlled drug release, nanosphere, nosocomial infections, titanium

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Authors: Monalisa Pradhan, Ajana Dutta, Irshad Kariyattuparamb Abbas, Boby Joseph, T. N. Guru Row, Diptikanta Swain, Gopal K. Pradhan

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Compounds with the Vanthoffite crystal structure having general formula Na6M(SO₄)₄ (M= Mg, Mn, Ni , Co, Fe, Cu and Zn) display a variety of intriguing physical properties intimately related to their structural arrangements. The compound Na6Mn(SO4)4 shows antiferromagnetic ordering at low temperature where the in-plane Mn-O•••O-Mn interactions facilitates antiferromagnetic ordering via a super-exchange interaction between the Mn atoms through the oxygen atoms . The inter-atomic bond distances and angles can easily be tuned by applying external pressure and can be probed using high resolution X-ray diffraction. Moreover, because the magnetic interaction among the Mn atoms are super-exchange type via Mn-O•••O-Mn path, the variation of the Mn-O•••O-Mn dihedral angle and Mn-O bond distances under high pressure inevitably affects the magnetic properties. Therefore, it is evident that high pressure studies on the magnetically ordered materials would shed light on the interplay between their structural properties and magnetic ordering. This will indeed confirm the role of buckling of the Mn-O polyhedral in understanding the origin of anti-ferromagnetism. In this context, we carried out the pressure dependent X-ray diffraction measurement in a diamond anvil cell (DAC) up to a maximum pressure of 17 GPa to study the phase transition and determine equation of state from the volume compression data. Upon increasing the pressure, we didn’t observe any new diffraction peaks or sudden discontinuity in the pressure dependences of the d values up to the maximum achieved pressure of ~17 GPa. However, it is noticed that beyond 12 GPa the a and b lattice parameters become identical while there is a discontinuity in the β value around the same pressure. This indicates a subtle transition to a pseudo-monoclinic phase. Using the third order Birch-Murnaghan equation of state (EOS) to fit the volume compression data for the entire range, we found the bulk modulus (B0) to be 44 GPa. If we consider the subtle transition at 12 GPa, we tried to fit another equation state for the volume beyond 12 GPa using the second order Birch-Murnaghan EOS. This gives a bulk modulus of ~ 34 GPa for this phase.

Keywords: mineral, structural phase transition, high pressure XRD, spectroscopy

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Authors: Minhal Abidi, Moinuddin

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Diabetes mellitus (DM) induced metabolic abnormalities causes oxidative stress which leads to the pathogenesis of complications associated with diabetes like retinopathy, nephropathy periodontitis etc. Combination of glycation and oxidation 'glycoxidation' occurs when oxidative reactions affect the early state of glycation products. Low density lipoprotein (LDL) is prone to glycoxidative attack by sugars and methylglyoxal (MGO) being a strong glycating agent may have severe impact on its structure and consequent role in diabetes. Pro-inflammatory cytokines like IL1β and TNFα produced by the action of gram negative bacteria in periodontits (PD) can in turn lead to insulin resistance. This work discusses modifications to LDL as a result of glycoxidation. The changes in the protein molecule have been characterized by various physicochemical techniques and the immunogenicity of the modified molecules was also evaluated as they presented neo-epitopes. Binding of antibodies present in diabetes patients to the native and glycated LDL has been evaluated. Role of modified epitopes in the generation of antibodies in diabetes and periodontitis has been discussed. The structural perturbations induced in LDL were analyzed by UV–Vis, fluorescence, circular dichroism and FTIR spectroscopy, molecular docking studies, thermal denaturation studies, Thioflavin T assay, isothermal titration calorimetry, comet assay. MALDI-TOF, ketoamine moieties, carbonyl content and HMF content were also quantitated in native and glycated LDL. IL1β and TNFα levels were also measured in the type 2 DM and PD patients. We report increased carbonyl content, ketoamine moieties and HMF content in glycated LDL as compared to native analogue. The results substantiate that in hyperglycemic state MGO modification of LDL causes structural perturbations making the protein antigenic which could obstruct normal physiological functions and might contribute in the development of secondary complications in diabetic patients like periodontitis.

Keywords: advanced glycation end products, diabetes mellitus, glycation, glycoxidation, low density lipoprotein, periodontitis

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Authors: Yasaman Samani, Ali Golmohammadi

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Introduction: The degree of conversion and depth of cure affects the clinical success of resin composite restorations directly. One of the main challenges in achieving a successful composite restoration is the achievement of sufficient depth of cure. The insufficient polymerization may lead to a decrease in the physical/mechanical and biological properties of resin composites and, as a result of that, unsuccessful composite restoration. Thus, because of the importance of studying and evaluating the depth of cure and degree of conversion in bulk-fill composites, we decided to evaluate and compare the degree of conversion and depth of cure in two bulk-fill composites; x-tra fill (Voco, Germany) and Opus Bulk fill APS (FGM, Brazil). Materials and Methods: Composite resin specimens (n=10) per group were prepared as cylinder blocks (4×8 mm) with bulk-fill composites, x-tra fil (Voco, Germany) designated as Group A, and Opus Bulk fill APS (FGM, Brazil) designated as Group B. Depth of cure was determined according to “ISO 4049; Depth of Cure” method, In which each specimen were cured (iLED, Woodpecker, China) 40 seconds and FTIR spectroscopy method was used to estimate the degree of conversion of both the bulk-fill composites. The degree of conversion of monomer to polymer was estimated individually in the coronal half (Group A1 and B1) and pulpal half (Group A2 and Group B2) by dividing each specimen into two halves. The data were analyzed using a Student’s t-test and one-way ANOVA at a 5% level of significance. Results: The mean depth of cure in x-tra fil (Voco, Germany) was 3.99 (±0.16), and for Opus Bulk fill, APS (FGM, Brazil) was 2.14 (±0.3). The degree of conversion percentage in Group A1 was 82.7 (±6.1), in group A2 was 73.4 (±5.2), in group B1 was 63.3 (±4.7) and in Group B2 was 56.5 (±7.7). Statistical analysis revealed a significant difference in the depth of cure between the two bulk-fill composites with x-tra fil (Voco, Germany) higher than Opus Bulk fill APS (FGM, Brazil) (P<0.001). The degree of conversion percentage also showed a significant difference, Group A1 being higher than A2 (P=0.0085), B1, and B2 (P<0.001). Group A2 was also higher than B1 (P=0.003) and B2 (P<0.001). There was no significant difference between B1 and B2 (P=0.072). Conclusion: The results indicate that x-tra fill has more depth of cure and a higher percentage of the degree of conversion than Opus Bulk fill APS. The coronal half of x-tra fil had the highest depth of cure percentage (82.66%), and the pulpal half of Opus Bulk fill APS had the lowest percentage (56.45%). Even though both bulk-fill composite materials had an acceptable degree of conversion (55% and higher), x-tra fill has shown better results.

Keywords: depth of cure, degree of conversion, bulk-fill composite, FTIR

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Authors: M. Jerold, V. Sivasubramanian, A. George, B.S. Ashik, S. S. Kumar

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Bioethanol is a sustainable biofuel that can be used alternative to fossil fuels. Today, third generation (3G) biofuel is gaining more attention than first and second-generation biofuel. The more lignin content in the lignocellulosic biomass is the major drawback of second generation biofuels. Algae are the renewable feedstock used in the third generation biofuel production. Algae contain a large number of carbohydrates, therefore it can be used for the fermentation by hydrolysis process. There are two groups of Algae, such as micro and macroalgae. In the present investigation, Macroalgae was chosen as raw material for the production of bioethanol. Two marine algae viz. Ulva Lactuca and Sargassum swartzii were used for the experimental studies. The algal biomass was characterized using various analytical techniques like Elemental Analysis, Scanning Electron Microscopy Analysis and Fourier Transform Infrared Spectroscopy to understand the physio-Chemical characteristics. The batch experiment was done to study the hydrolysis and operation parameters such as pH, agitation, fermentation time, inoculum size. The saccharification was done with acid and alkali treatment. The experimental results showed that NaOH treatment was shown to enhance the bioethanol. From the hydrolysis study, it was found that 0.5 M Alkali treatment would serve as optimum concentration for the saccharification of polysaccharide sugar to monomeric sugar. The maximum yield of bioethanol was attained at a fermentation time of 9 days. The inoculum volume of 1mL was found to be lowest for the ethanol fermentation. The agitation studies show that the fermentation was higher during the process. The percentage yield of bioethanol was found to be 22.752% and 14.23 %. The elemental analysis showed that S. swartzii contains a higher carbon source. The results confirmed hydrolysis was not completed to recover the sugar from biomass. The specific gravity of ethanol was found to 0.8047 and 0.808 for Ulva Lactuca and Sargassum swartzii, respectively. The purity of bioethanol also studied and found to be 92.55 %. Therefore, marine algae can be used as a most promising renewable feedstock for the production of bioethanol.

Keywords: algae, biomass, bioethaol, biofuel, pretreatment

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Authors: Luciana P. Mazur, Tatiana A. Pozdniakova, Rui A. R. Boaventura, Vitor J. P. Vilar

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The principal mechanism of metal ions sequestration by brown algae involves the formation of complexes between the metal ion and functional groups present on the cell wall of the biological material. To understand the role of functional groups on copper(II) uptake by Ascophyllum nodosum, some functional groups were chemically modified. The esterification of carboxylic groups was carried out by suspending the biomass in a methanol/HCl solution under stirring for 48 h and the blocking of the sulfonic groups was performed by repeating the same procedure for 4 cycles of 48 h. The methylation of amines was conducted by suspending the biomass in a formaldehyde/formic acid solution under shaking for 6 h and the chemical modification of sulfhydryl groups on the biomass surface was achieved using dithiodipyridine for 1 h. Equilibrium sorption studies for Cu2+ using the raw and esterified algae were performed at pH 2.0 and 4.0. The experiments were performed using an initial copper concentration of 300 mg/L and algae dose of 1.0 g/L. After reaching the equilibrium, the metal in solution was quantified by atomic absorption spectrometry. The biological material was analyzed by Fourier Transform Infrared Spectroscopy and Potentiometric Titration techniques for functional groups identification and quantification, respectively. The results using unmodified algae showed that the maximum copper uptake capacity at pH 4.0 and 2.0 was 1.17 and 0.52 mmol/g, respectively. At acidic pH values most carboxyl groups are protonated and copper sorption suffered a significant reduction of 56%. Blocking the carboxylic, sulfonic, amines and sulfhydryl functional groups, copper uptake decreased by 24/26%, 69/81%, 1/23% and 40/27% at pH 2.0/4.0, respectively, when compared to the unmodified biomass. It was possible to conclude that the carboxylic and sulfonic groups are the main functional groups responsible for copper binding (>80%). This result is supported by the fact that the adsorption capacity is directly related to the presence of carboxylic groups of the alginate polymer, and the second most abundant acidic functional group in brown algae is the sulfonic acid of fucoidan that contributes, to a lower extent, to heavy metal binding, particularly at low pH.

Keywords: biosorption, brown marine macroalgae, copper, ion-exchange

Procedia PDF Downloads 298

Authors: Parvin Samadi Pakchin, Reza Saber, Hossein Ghanbari, Yadollah Omidi

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Ovarian cancer is one of the leading cause of mortality among the gynecological malignancies, and it remains the one of the most prevalent cancer in females worldwide. Tumor markers are biochemical molecules in blood or tissues which can indicates cancers occurrence in the human body. So, the sensitive and specific detection of cancer markers typically recruited for diagnosing and evaluating cancers. Recently extensive research efforts are underway to achieve a simple, inexpensive and accurate device for detection of cancer biomarkers. Compared with conventional immunoassay techniques, electrochemical immunosensors are of great interest, because they are specific, simple, inexpensive, easy to handling and miniaturization. Moreover, in the past decade nanotechnology has played a crucial role in the development of biosensors. In this study, a signal-off electrochemical immunosensor for the detection of CA125 antigen has been developed using chitosan-gold nanoparticles (CS-AuNP) and multi-wall carbon nanotubes (MWCNT) composites. Toluidine blue (TB) is used as redox probe which is immobilized on the electrode surface. CS-AuNP is synthesized by a simple one step method that HAuCl4 is reduced by NH2 groups of chitosan. The CS-AuNP-MWCNT modified electrode has shown excellent electrochemical performance compared with bare Au electrode. MWCNTs and AuNPs increased electrochemical conductivity and accelerate electrons transfer between solution and electrode surface while excessive amine groups on chitosan lead to the effective loading of the biological material (CA125 antibody) and TB on the electrode surface. The electrochemical, immobilization and sensing properties CS-AuNP-MWCNT-TB modified electrodes are characterized by cyclic voltammetry, electrochemical impedance spectroscopy, differential pulse voltammetry and square wave voltammetry with Fe(CN)63−/4−as an electrochemical redox indicator.

Keywords: signal-off electrochemical biosensor, CA125, ovarian cancer, chitosan-gold nanoparticles

Procedia PDF Downloads 265

Authors: Qianying Sun, Abdelhadi Kassiba, Guorong Li

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ZnO with wurtzite structure is a well-known semiconducting oxide (SCO), being applied in thermoelectric devices, varistors, gas sensors, transparent electrodes, solar cells, liquid crystal displays, piezoelectric and electro-optical devices. Intrinsically, ZnO is weakly n-type SCO due to native defects (Znⱼ, Vₒ). However, the substitutional doping by metallic elements as (Al, Ti) gives rise to a high n-type conductivity ensured by donor centers. Under CO+N₂ sintering atmosphere, Schottky barriers of ZnO ceramics will be suppressed by lowering the concentration of acceptors at grain boundaries and then inducing a large increase in the Hall mobility, thereby increasing the conductivity. The presented work concerns ZnO based ceramics, which are fabricated with doping by TiO₂ (0.50mol%), Al₂O₃ (0.25mol%) and MgO (1.00mol%) and sintering in different atmospheres (Air (A), N₂ (N), CO+N₂(C)). We obtained uniform, dense ceramics with ZnO as the main phase and Zn₂TiO₄ spinel as a secondary and minor phase. An important increase of the conductivity was shown for the samples A, N, and C which were sintered under different atmospheres. The highest conductivity (σ = 1.52×10⁵ S·m⁻¹) was obtained under the reducing atmosphere (CO). The role of doping was investigated with the aim to identify the local environment and valence states of the doping elements. Thus, Electron paramagnetic spectroscopy (EPR) determines the concentration of defects and the effects of charge carriers in ZnO ceramics as a function of the sintering atmospheres. The relation between conductivity and defects concentration shows the opposite behavior between these parameters suggesting that defects act as traps for charge carriers. For Al ions, nuclear magnetic resonance (NMR) technique was used to identify the involved local coordination of these ions. Beyond the six and forth coordinated Al, an additional NMR signature of ZnO based TCO requires analysis taking into account the grain boundaries and the conductivity through the Knight shift effects. From the thermal evolution of the conductivity as a function of the sintering atmosphere, we succeed in defining the conditions to realize ZnO based TCO ceramics with an important thermal coefficient of resistance (TCR) which is promising for electrical safety of devices.

Keywords: ceramics, conductivity, defects, TCO, ZnO

Procedia PDF Downloads 163

Authors: Lucja Rodzik, Joanna Lewandowska-Lancucka, Michal Szuwarzynski, Krzysztof Szczubialka, Maria Nowakowska

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The analysis of nucleobases is of great importance for bioscience since their abnormal concentration in body fluids suggests the deficiency and mutation of the immune system, and it is considered to be an important parameter for diagnosis of various diseases. The presented conjugate meets the need for development of the effective, selective and highly sensitive sensor for nucleobase/nucleoside detection. The novel, highly fluorescent cadmium telluride quantum dots (CdTe QDs) functionalized with thymine and stabilized with thioglycolic acid (TGA) conjugates has been developed and thoroughly characterized. Successful formation of the material was confirmed by elemental analysis, and UV–Vis fluorescence and FTIR spectroscopies. The crystalline structure of the obtained product was characterized with X-ray diffraction (XRD) method. The composition of CdTe QDs and their thymine conjugate was also examined using X-ray photoelectron spectroscopy (XPS). The size of the CdTe-thymine was 3-6 nm as demonstrated using atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM) imaging. The plasmon resonance fluorescence band at 540 nm on excitation at 351 nm was observed for these nanoparticles. The intensity of this band increased with the increase in the amount of conjugated thymine with no shift in its position. Based on the fluorescence measurements, it was found that the CdTe-thymine conjugate interacted efficiently and selectively not only with adenine, a nucleobase complementary to thymine, but also with nucleosides and adenine-containing modified nucleosides, i.e., 5′-deoxy-5′-(methylthio)adenosine (MTA) and 2’-O-methyladenosine, the urinary tumor markers which allow monitoring of the disease progression. The applicability of the CdTe-thymine sensor for the real sample analysis was also investigated in simulated urine conditions. High sensitivity and selectivity of CdTe-thymine fluorescence towards adenine, adenosine and modified adenosine suggest that obtained conjugate can be potentially useful for development of the biosensor for complementary nucleobase/nucleoside detection.

Keywords: CdTe quantum dots, conjugate, sensor, thymine

Procedia PDF Downloads 379

Authors: Krasimira N. Zhilkova, Mariya K. Kyulavska, Roza P. Mateva

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The anionic polymerization of -caprolactam (CL) with bifunctional activators has been extensively studied as an effective and beneficial method of improving chemical and impact resistances, elasticity and other mechanical properties of polyamide (PA6). In presence of activators or macroactivators (MAs) also called polymeric activators (PACs) the anionic polymerization of lactams proceeds rapidly at a temperature range of 130-180C, well below the melting point of PA-6 (220C) permitting thus the direct manufacturing of copolymer product together with desired modifications of polyamide properties. Copolymers of PA6 with an elastic polypropylene glycol (PPG) middle block into main chain were successfully synthesized via activated anionic ring opening polymerization (ROP) of CL. Using novel PACs based on PPG polyols (with differ molecular weight) the anionic ROP of CL was realized and investigated in the presence of a basic initiator sodium salt of CL (NaCL). The PACs were synthesized as N-carbamoyllactam derivatives of hydroxyl terminated PPG functionalized with isophorone diisocyanate [IPh, 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane] and blocked then with CL units via an addition reaction. The block copolymers were analyzed and proved with 1H-NMR and FT-IR spectroscopy. The influence of the CL/PACs ratio in feed, the length of the PPG segments and polymerization conditions on the kinetics of anionic ROP, on average molecular weight, and on the structure of the obtained block copolymers were investigated. The structure and phase behaviour of the copolymers were explored with differential scanning calorimetry, wide-angle X-ray diffraction, thermogravimetric analysis and dynamic mechanical thermal analysis. The crystallinity dependence of PPG content incorporated into copolymers main backbone was estimate. Additionally, the mechanical properties of the obtained copolymers were studied by notched impact test. From the performed investigation in this study could be concluded that using PPG based PACs at the chosen ROP conditions leads to obtaining well-defined PA6-b-PPG-b-PA6 copolymers with improved impact resistance.

Keywords: anionic ring opening polymerization, caprolactam, polyamide copolymers, polypropylene glycol

Procedia PDF Downloads 387

Authors: Anna S. Tolkacheva, Sergey N. Shkerin, Kirill G. Zemlyanoi, Olga G. Reznitskikh, Pavel D. Khavlyuk

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Calcium oxovanadates with garnet related structure are multifunctional oxides in various fields like photoluminescence, microwave dielectrics, and magneto-dielectrics. For example, vanadate garnets are self-luminescent compounds. They attract attention as RE-free broadband excitation and emission phosphors and are candidate materials for UV-based white light-emitting diodes (WLEDs). Ca₅M₄(VO₄)₆ (M = Mg, Zn, Co, Ni, Mn) compounds are also considered promising for application in microwave devices as substrate materials. However, the relation between their structure, composition and physical/chemical properties remains unclear. Given the above-listed observations, goals of this study are to synthesise Ca₅M₄(VO₄)₆ (M = Mg, Zn, Ni) and to study their thermal and electrical properties. Solid solutions Ca₅Mg₄₋ₓMₓ(VO₄)₆ (0 ≤ x ≤ 4) where M is Zn and Ni have been synthesized by sol-gel method. The single-phase character of the final products was checked by powder X-ray diffraction on a Rigaku D/MAX-2200 X-ray diffractometer using Cu Kα radiation in the 2θ range from 15° to 70°. The dependence of thermal properties on chemical composition of solid solutions was studied using simultaneous thermal analyses (DSC and TG). Thermal analyses were conducted in a Netzch simultaneous analyser STA 449C Jupiter, in Ar atmosphere, in temperature range from 25 to 1100°C heat rate was 10 K·min⁻¹. Coefficients of thermal expansion (CTE) were obtained by dilatometry measurements in air up to 800°C using a Netzsch 402PC dilatometer; heat rate was 1 K·min⁻¹. Impedance spectra were obtained via the two-probe technique with an impedance meter Parstat 2273 in air up to 700°C with the variation of pH₂O from 0.04 to 3.35 kPa. Cation deficiency in Ca and Mg sublattice under the substitution of MgO with ZnO up to 1/6 was observed using Rietveld refinement of the crystal structure. Melting point was found to decrease with x changing from 0 to 4 in Ca₅Mg₄₋ₓMₓ(VO₄)₆ where M is Zn and Ni. It was observed that electrical conductivity does not depend on air humidity. The reported study was funded by the RFBR Grant No. 17–03–01280. Sample attestation was carried out in the Shared Access Centers at the IHTE UB RAS.

Keywords: garnet structure, electrical conductivity, thermal expansion, thermal properties

Procedia PDF Downloads 136

Authors: Mehrnaz Mostafavi

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Lung cancer is one of the most harmful forms of cancer. The long-term survival rate of lung cancer patients treated by conventional modalities such as surgical resection, radiation, and chemotherapy remains far from satisfactory. Systemic drug delivery is rarely successful because only a limited amount of the chemotherapeutic drug targets lung tumor sites, even when administered at a high dose. Targeted delivery of drug molecules to organs or special sites is one of the most challenging research areas in pharmaceutical sciences. By developing colloidal delivery systems such as liposomes, micelles and nanoparticles a new frontier was opened for improving drug delivery. Nanoparticles with their special characteristics such as small particle size, large surface area and the capability of changing their surface properties have numerous advantages compared with other delivery systems. Targeted nanoparticle delivery to the lungs is an emerging area of interest.Multimodal or combination therapy represents a promising new method to fight disease. Therefore, a combination of different therapeutic strategies may be the best alternative to improve treatment outcomes for lung cancer. Photothermal therapy was proposed as a novel approach to treatment. In this work, photothermal therapy with gold nanoparticles and near infrared laser (NIR) irradiation was investigated.Four types of small (<100nm), NIR absorbing gold nanoparticles (nanospheres, nanorods) were synthesized using wet chemical methods and characterized by transmission electron microscopy, dynamic light scattering and UV-vis spectroscopy. Their synthesis and properties were evaluated, to determine their feasibility as a photothermal agent for clinical applications. In vitro cellular uptake studies of the nanoparticles into lung cancer cell lines was measured using light scattering microscopy.Small gold nanorods had good photothermal properties and the greatest cellular uptake, and were used in photothermal studies. Under 4W laser irradiation, an increase in temperature of 10°C and decrease in cell viability of up to 80% were obtained.

Keywords: photothermal, therapy, cancer, gold nanorods

Procedia PDF Downloads 223

Authors: Fabrizio Ascione, Martina Borrelli, Rosa Francesca De Masi, Silvia Ruggiero, Giuseppe Peter Vanoli

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The Directive 2010/31/EC 'Directive of the European Parliament and of the Council of 19 may 2010 on the energy performance of buildings' moved the targets of the previous version toward more ambitious targets, for instance by establishing that, by 31 December 2020, all new buildings should demand nearly zero-energy. Moreover, the demonstrative role of public buildings is strongly affirmed so that also the target nearly zero-energy buildings is anticipated, in January 2019. On the other hand, given the very low turn-over rate of buildings (in Europe, it ranges between 1-3%/yearly), each policy that does not consider the renovation of the existing building stock cannot be effective in the short and medium periods. According to this proposal, the study provides a novel, holistic approach to design the refurbishment of educational buildings in colder cities of Mediterranean regions enabling stakeholders to understand the uncertainty to use numerical modelling and the real environmental and economic impacts of adopting some energy efficiency technologies. The case study is a university building of Molise region in the centre of Italy. The proposed approach is based on the application of the cost-optimal methodology as it is shown in the Delegate Regulation 244/2012 and Guidelines of the European Commission, for evaluating the cost-optimal level of energy performance with a macroeconomic approach. This means that the refurbishment scenario should correspond to the configuration that leads to lowest global cost during the estimated economic life-cycle, taking into account not only the investment cost but also the operational costs, linked to energy consumption and polluting emissions. The definition of the reference building has been supported by various in-situ surveys, investigations, evaluations of the indoor comfort. Data collection can be divided into five categories: 1) geometrical features; 2) building envelope audit; 3) technical system and equipment characterization; 4) building use and thermal zones definition; 5) energy building data. For each category, the required measures have been indicated with some suggestions for the identifications of spatial distribution and timing of the measurements. With reference to the case study, the collected data, together with a comparison with energy bills, allowed a proper calibration of a numerical model suitable for the hourly energy simulation by means of EnergyPlus. Around 30 measures/packages of energy, efficiency measure has been taken into account both on the envelope than regarding plant systems. Starting from results, two-point will be examined exhaustively: (i) the importance to use validated models to simulate the present performance of building under investigation; (ii) the environmental benefits and the economic implications of a deep energy refurbishment of the educational building in cold climates.

Keywords: energy simulation, modelling calibration, cost-optimal retrofit, university building

Procedia PDF Downloads 155

Authors: Mahfouz Saeed

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Cu₂(ZnSn)(S)₄ (CTZS) offers potential advantages over CuInGaSe₂ (CIGS) as solar thin film because to its higher band gap. Preparing such photovoltaic materials by electrochemical techniques is particularly attractive due to the lower processing cost and the high throughput of such techniques. Several recent publications report CTZS electroplating; however, the electrochemical process still facing serious challenges such as a sulfur atomic ration which is about 50% of the total alloy. We introduce in this work an improved electrolyte composition which enables the direct electrodeposition of CTZS from a single bath. The electrolyte is significantly more dilute in comparison to common baths described in the literature. The bath composition we introduce is: 0.0032 M CuSO₄, 0.0021 M ZnSO₄, 0.0303 M SnCl₂, 0.0038 M Na₂S₂O₃, and 0.3 mM Na₂S₂O3. PHydrion is applied to buffer the electrolyte to pH=2, and 0.7 M LiCl is applied as supporting electrolyte. Electrochemical process was carried at a rotating disk electrode which provides quantitative characterization of the flow (room temperature). Comprehensive electrochemical behavior study at different electrode rotation rates are provided. The effects of agitation on atomic composition of the deposit and its adhesion to the molybdenum back contact are discussed. The post treatment annealing was conducted under sulfur atmosphere with no need for metals addition from the gas phase during annealing. The potential which produced the desired atomic ratio of CTZS at -0.82 V/NHE. Smooth deposit, with uniform composition across the sample surface and depth was obtained at 500 rpm rotation speed. Final sulfur atomic ratio was adjusted to 50.2% in order to have the desired atomic ration. The final composition was investigated using Energy-dispersive X-ray spectroscopy technique (EDS). XRD technique used to analyze CTZS crystallography and thickness. Complete and functional CTZS PV devices were fabricated by depositing all the required layers in the correct order and the desired optical properties. Acknowledgments: Case Western Reserve University for the technical help and for using their instruments.

Keywords: photovoltaic, CTZS, thin film, electrochemical

Procedia PDF Downloads 218

Authors: Laura Bravo-García, Gotzone Barandika, Begoña Bazán, M. Karmele Urtiaga, Luis M. Lezama, María I. Arriortua

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Solid coordination networks (SCNs) are materials consisting of metal ions or clusters that are linked by polyfunctional organic ligands and can be designed to form tridimensional frameworks. Their structural features, as for example high surface areas, thermal stability, and in other cases large cavities, have opened a wide range of applications in fields like drug delivery, host-guest chemistry, biomedical imaging, chemical sensing, heterogeneous catalysis and others referred to greenhouse gases storage or even separation. In this sense, the use of polycarboxylate anions and dipyridyl ligands is an effective strategy to produce extended structures with the needed characteristics for these applications. In this context, a novel compound, [Cu4(m-BDC)4(bpa)2DMF]•DMF has been obtained by microwave synthesis, where m-BDC is 1,3-benzenedicarboxylate and bpa 1,2-bis(4-pyridyl)ethane. The crystal structure can be described as a three dimensional framework formed by two equal, interpenetrated networks. Each network consists of two different CuII dimers. Dimer 1 have two coppers with a square pyramidal coordination, and dimer 2 have one with a square pyramidal coordination and other with octahedral one, the last dimer is unique in literature. Therefore, the combination of both type of dimers is unprecedented. Thus, benzenedicarboxylate ligands form sinusoidal chains between the same type of dimers, and also connect both chains forming these layers in the (100) plane. These layers are connected along the [100] direction through the bpa ligand, giving rise to a 3D network with 10 Å2 voids in average. However, the fact that there are two interpenetrated networks results in a significant reduction of the available volume. Structural analysis was carried out by means of single crystal X-ray diffraction and IR spectroscopy. Thermal and magnetic properties have been measured by means of thermogravimetry (TG), X-ray thermodiffractometry (TDX), and electron paramagnetic resonance (EPR). Additionally, CO2 and CH4 high pressure adsorption measurements have been carried out for this compound.

Keywords: gas adsorption, interpenetrated networks, magnetic measurements, solid coordination network (SCN), thermal stability

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Authors: Barbara Urasinska-Wojcik, Neil Chilton, Peter Todd, Christopher Elsworthy, Gregory J. Gibbons

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The recent increase in the application of Additive Manufacturing (AM) of products has resulted in new demands on capability. The ability to integrate both form and function within printed objects is the next frontier in the 3D printing area. To move beyond prototyping into low volume production, we demonstrate a UK-designed and built AM hybrid system that combines polymer based structural deposition with digital deposition of electrically conductive elements. This hybrid manufacturing system is based on a multi-planar build approach to improve on many of the limitations associated with AM, such as poor surface finish, low geometric tolerance, and poor robustness. Specifically, the approach involves a multi-planar Material Extrusion (ME) process in which separated build stations with up to 5 axes of motion replace traditional horizontally-sliced layer modeling. The construction of multi-material architectures also involved using multiple print systems in order to combine both ME and digital deposition of conductive material. To demonstrate multi-material 3D printing, three thermoplastics, acrylonitrile butadiene styrene (ABS), polyamide 6,6/6 copolymers (CoPA) and polyamide 12 (PA) were used to print specimens, on top of which our high viscosity Ag-particulate ink was printed in a non-contact process, during which drop characteristics such as shape, velocity, and volume were assessed using a drop watching system. Spectroscopic analysis of these 3D printed materials in the IR region helped to determine the optimum in-situ curing system for implementation into the AM system to achieve improved adhesion and surface refinement. Thermal Analyses were performed to determine the printed materials glass transition temperature (Tg), stability and degradation behavior to find the optimum annealing conditions post printing. Electrical analysis of printed conductive tracks on polymer surfaces during mechanical testing (static tensile and 3-point bending and dynamic fatigue) was performed to assess the robustness of the electrical circuits. The tracks on CoPA, ABS, and PA exhibited low electrical resistance, and in case of PA resistance values of tracks remained unchanged across hundreds of repeated tensile cycles up to 0.5% strain amplitude. Our developed AM printer has the ability to fabricate fully functional objects in one build, including complex electronics. It enables product designers and manufacturers to produce functional saleable electronic products from a small format modular platform. It will make 3D printing better, faster and stronger.

Keywords: additive manufacturing, conductive tracks, hybrid 3D printer, integrated manufacture

Procedia PDF Downloads 144

Authors: John Olorunfemi Abe, Olawale Muhammed Popoola, Abimbola Patricia Idowu Popoola

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Hydrogen is an appealing alternative to fossil fuels because of its abundance, low weight, high energy density, and relative lack of contaminants. However, its low density presents a number of storage challenges. Therefore, this work studies the influence of refractory nitride additives consisting of 5 wt. % each of hexagonal boron nitride (h-BN), titanium nitride (TiN), and aluminum nitride (AlN) on hydrogen storage and electrochemical characteristics of Ti6Al4V-based materials produced by spark plasma sintering. The microstructure and phase constituents of the sintered materials were characterized using scanning electron microscopy (in conjunction with energy-dispersive spectroscopy) and X-ray diffraction, respectively. Pressure-composition-temperature (PCT) measurements were used to assess the hydrogen absorption/desorption behavior, kinetics, and storage capacities of the sintered materials, respectively. The pure Ti6Al4V alloy displayed a two-phase (α+β) microstructure, while the modified composites exhibited apparent microstructural modifications with the appearance of nitride-rich secondary phases. It is found that the diffusion process controls the kinetics of the hydrogen absorption. Thus, a faster rate of hydrogen absorption at elevated temperatures ensued. The additives acted as catalysts, lowered the activation energy and accelerated the rate of hydrogen sorption in the composites relative to the monolithic alloy. Ti6Al4V-5 wt. % h-BN appears to be the most promising candidate for hydrogen storage (2.28 wt. %), followed by Ti6Al4V-5 wt. % TiN (2.09 wt. %), whereas Ti6Al4V-5 wt. % AlN shows the least hydrogen storage performance (1.35 wt. %). Accordingly, the developed hydride system (Ti6Al4V-5h-BN) may be competitive for use in applications involving short-range continuous vehicles (~50-100km) as well as stationary applications such as electrochemical devices, large-scale storage cylinders in hydrogen production locations, and hydrogen filling stations.

Keywords: hydrogen storage, Ti6Al4V hydride system, pressure-composition-temperature measurements, refractory nitride additives, spark plasma sintering, Ti6Al4V-based materials

Procedia PDF Downloads 36

Authors: Lidya Hailu, Ramesh Duraisamy, Masood Akhtar Khan, Belete Yilma

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Disposable food packaging is a single-use plastics that can include any disposable plastic item which could be designed and use only once. In this context, this study aimed to prepare and evaluate bioplastic food packaging material from avocado seed starch and sugarcane bagasse cellulose and to characterise avocado seed starch. Performed the physicomechanical, structural, thermal properties, and biodegradability of raw materials and readily prepared bioplastic using the universal tensile testing machine, FTIR, UV-Vis spectroscopy, TGA, XRD, and SEM. Results have shown that an increasing amount of glycerol (3-5 mL) resulted in increases in water absorption, density, water vapor permeability, and elongation at the break of prepared bioplastic. However, it causes decreases in % transmittance, thermal degradation, and the tensile strength of prepared bioplastic. Likewise, the addition of cellulose fiber (0-15 %) increases % transmittance ranged (91.34±0.12-63.03±0.05 %), density (0.93±0.04-1.27±0.02 g/cm3), thermal degradation (310.01-321.61°C), tensile strength (2.91±6.18-4.21±6.713 MPa) of prepared bioplastic. On the other hand, it causes decreases in water absorption (14.4±0.25-9.40±0.007 %), water vapor permeability (9.306x10-12±0.3-3.57x10-12±0.15 g•s−1•m−1•Pa−1) and elongation at break (34.46±3.37-27.63±5.67 %) of prepared bioplastic. All the readily prepared bioplastic films rapidly degraded in the soil in the first 6 days and decompose within 12 days with a diminutive leftover and completely degraded within 15 days under an open soil atmosphere. Studied results showed starch derived bioplastic reinforced with 15 % cellulose fiber that plasticized with 3 mL of glycerol had improved results than other combinations of glycerol and bagasse cellulose with avocado seed starch. Thus, biodegradable disposable food packaging cup has been successfully produced in the lab-scale level using the studied approach. Biodegradable disposable food packaging materials have been successfully produced by employing avocado seed starch and sugarcane bagasse cellulose. The future study should be done on nano scale production since this study was done at the micro level.

Keywords: avocado seed, food packaging, glycerol, sugarcane bagasse

Procedia PDF Downloads 310

Authors: Abdul Mutalib Md Jani, Abdul Hadi Mahmud, Mohd Tajuddin Mohd Ali

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The rapid growth of interest in surface modification of nanostructures materials that exhibit improved structural and functional properties is attracting more researchers. The unique properties of highly ordered nanoporous anodic aluminium oxide (NAAO) membrane have been proposed as a platform for biosensing applications. They exhibit excellent physical and chemical properties with high porosity, high surface area, tunable pore sizes and excellent chemical resistance. In this study, NAAO was functionalized with 3-aminopropyltriethoxysilane (APTES) to prepared silane-modified NAAO. Amine functional groups are formed on the surface of NAAO during silanization and were characterized using Fourier Transform Infrared spectroscopy (FTIR). The synthesis of multi segment of peptide on NAAO surfaces can be realized by changing the surface chemistry of the NAAO membrane via click chemistry. By click reactions, utilizing alkyne terminated with amino group, various peptides tagged on NAAO can be envisioned from chiral natural or unnatural amino acids using standard coupling methods (HOBt, EDCI and HBTU). This strategy seemly versatile since coupling strategy of dipeptide with another amino acids, leading to tripeptide, tetrapeptide or pentapeptide, can be synthesized without purification. When an appropriate terminus is selected, multiple segments of amino acids can be successfully synthesized on the surfaces. The immobilized NAAO should be easily separated from the reaction medium by conventional filtration, thus avoiding complicated purification methods. Herein, we proposed to synthesize multi fragment peptide as a model for capturing and attaching various small biomolecules on NAAO surfaces and can be also applied as biosensing device, drug delivery systems and biocatalyst.

Keywords: nanoporous anodic aluminium oxide, silanization, peptide synthesise, click chemistry

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Authors: Elmira Solati, Atousa Mehrani, Davoud Dorranian

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Generation of ZnO-Au nanocomposite under laser irradiation of a mixture of the ZnO and Au colloidal suspensions are experimentally investigated. In this work, firstly ZnO and Au nanoparticles are prepared by pulsed laser ablation of the corresponding metals in water using the 1064 nm wavelength of Nd:YAG laser. In a second step, the produced ZnO and Au colloidal suspensions were mixed in different volumetric ratio and irradiated using the second harmonic of a Nd:YAG laser operating at 532 nm wavelength. The changes in the size of the nanostructure and optical properties of the ZnO-Au nanocomposite are studied as a function of the volumetric ratio of ZnO and Au colloidal suspensions. The crystalline structure of the ZnO-Au nanocomposites was analyzed by X-ray diffraction (XRD). The optical properties of the samples were examined at room temperature by a UV-Vis-NIR absorption spectrophotometer. Transmission electron microscopy (TEM) was done by placing a drop of the concentrated suspension on a carbon-coated copper grid. To further confirm the morphology of ZnO-Au nanocomposites, we performed Scanning electron microscopy (SEM) analysis. Room temperature photoluminescence (PL) of the ZnO-Au nanocomposites was measured to characterize the luminescence properties of the ZnO-Au nanocomposites. The ZnO-Au nanocomposites were characterized by Fourier transform infrared (FTIR) spectroscopy. The X-ray diffraction pattern shows that the ZnO-Au nanocomposites had the polycrystalline structure of Au. The behavior observed by images of transmission electron microscope reveals that soldering of Au and ZnO nanoparticles include their adhesion. The plasmon peak in ZnO-Au nanocomposites was red-shifted and broadened in comparison with pure Au nanoparticles. By using the Tauc’s equation, the band gap energy for ZnO-Au nanocomposites is calculated to be 3.15–3.27 eV. In this work, the formation of ZnO-Au nanocomposites shifts the FTIR peak of metal oxide bands to higher wavenumbers. PL spectra of the ZnO-Au nanocomposites show that several weak peaks in the ultraviolet region and several relatively strong peaks in the visible region. SEM image indicates that the morphology of ZnO-Au nanocomposites produced in water was spherical. The TEM images of ZnO-Au nanocomposites demonstrate that with increasing the volumetric ratio of Au colloidal suspension the adhesion increased. According to the size distribution graphs of ZnO-Au nanocomposites with increasing the volumetric ratio of Au colloidal suspension the amount of ZnO-Au nanocomposites with the smaller size is further.

Keywords: Au nanoparticles, pulsed laser ablation, ZnO-Au nanocomposites, ZnO nanoparticles

Procedia PDF Downloads 311

Authors: Md. Refat Jahan Rakiba, M. Belal Hossaina, Rakesh Kumarc, Md. Akram Ullaha, Sultan Al Nahiand, Nazmun Naher Rimaa, Tasrina Rabia Choudhury, Samia Islam Libaf, Jimmy Yub, Mayeen Uddin Khandakerg, Abdelmoneim Suliemanh, Mohamed Mahmoud Sayedi

Abstract:

Microplastics (MPs) have become an emerging global pollutant due to their wide spread and dispersion and potential threats to marine ecosystems. However, studies on MPs of estuarine and coastal ecosystems of Bangladesh are very limited or not available. In this study, we conducted the first study on the abundance, distribution, characteristics and potential risk assessment of microplastics in the sediment of Karnaphuli River estuary, Bangladesh. Microplastic particles were extracted from sediments of 30 stations along the estuary by density separation, and then enumerated and characterize by using steromicroscope and Fourier Transform Infrared (FT-IR) spectroscopy. In the collected sediment, the number of MPs varied from 22.29 - 59.5 items kg−1 of dry weight (DW) with an average of 1177 particles kg−1 DW. The mean abundance was higher in the downstream and left bank of estuary where the predominant shape, colour, and size of MPs were films (35%), white (19%), and >5000 μm (19%), respectively. The main polymer types were polyethylene terephthalate, polystyrene, polyethylene, cellulose, and nylon. MPs were found to pose risks (low to high) in the sediment of the estuary, with the highest risk occuring at one station near a sewage outlet, according to the results of risk analyses using the pollution risk index (PRI), polymer risk index (H), contamination factors (CFs), and pollution load index (PLI). The single value index, PLI clearly demonastated that all sampling sites were considerably polluted (as PLI >1) with microplastics. H values showed toxic polymers even in lower proportions possess higher polymeric hazard scores and vice versa. This investigation uncovered new insights on the status of MPs in the sediments of Karnaphuli River estuary, laying the groundwork for future research and control of microplastic pollution and management.

Keywords: microplastics, polymers, pollution risk assessment, Karnaphuli esttuary

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